WO2025035779A1 - 一种量子点薄膜图案化方法与应用 - Google Patents

一种量子点薄膜图案化方法与应用 Download PDF

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WO2025035779A1
WO2025035779A1 PCT/CN2024/084578 CN2024084578W WO2025035779A1 WO 2025035779 A1 WO2025035779 A1 WO 2025035779A1 CN 2024084578 W CN2024084578 W CN 2024084578W WO 2025035779 A1 WO2025035779 A1 WO 2025035779A1
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quantum dot
patterning
thin film
quantum dots
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张昊
付钟
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Tsinghua University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene

Definitions

  • the present invention belongs to the field of optoelectronic technology, and in particular relates to a method for preparing a patterned quantum dot film and the construction of a light-emitting display device.
  • Quantum dots are semiconductor nanocrystals with a size smaller than the Bohr radius, with a common size of 2-20nm. They are composed of an inorganic semiconductor core and surface ligands, and have obvious volume effect, surface effect, size effect and other characteristics.
  • the emission wavelength can be controlled according to the size, the emission half-width is narrow, and the color gamut is wide.
  • quantum dots can form a stable colloidal solution, and low-cost, large-area, and high-efficiency optoelectronic devices can be constructed by solution method.
  • quantum dots are usually used as photoelectric active layers in the form of thin films.
  • Patterning methods can achieve the construction of quantum dot arrays with micrometer-scale resolution, which has broader application prospects in the fields of high-definition and colorful flat-panel displays or lighting, sensor imaging, photoelectric stimulation, etc.
  • Conventional quantum dot thin film patterning methods have defects. For example, photolithography technology is difficult to ensure the compatibility of quantum dots and photoresists, the pattern resolution achieved by inkjet printing technology is limited (>50 microns), and technologies such as electron beam or laser direct writing damage the photoelectric properties of quantum dots themselves.
  • CN114839835A uses photosensitive cross-linking molecules containing diazirine groups (i.e., carbene cross-linking molecules) to realize the patterning of quantum dot films.
  • the singlet carbene intermediates generated by the cross-linking molecules undergo insertion reactions with the carbon-hydrogen bonds in the surface ligands of the quantum dots, thereby cross-linking the quantum dots to achieve patterning.
  • the singlet carbene intermediates with higher energy (the net electron spin S in the molecule is 0) are easily converted to triplet states (the net electron spin S in the molecule is 1).
  • the triplet carbene produced reacts rapidly with oxygen in the air. This side reaction depletes the singlet carbene, and the quantum dots cannot be cross-linked to form patterns.
  • the purpose of the present invention is to provide a quantum dot thin film patterning method and application, which can realize efficient patterning of quantum dots of different types and compositions in the air, and has the advantages of high resolution, strong universality, and suitability for large-scale industrial production.
  • the present invention provides a method for patterning a quantum dot film, which comprises the following steps: (1) mixing quantum dots with a photosensitive crosslinker to form a thin layer; (2) performing a patterned exposure treatment on the thin layer to obtain a patterned quantum dot film; wherein the surface of the quantum dots has a ligand containing a carbon-hydrogen bond; and the photosensitive crosslinker has a structure shown in Formula I:
  • R1 is an electron-donating group
  • n ⁇ 2 is an electron-donating group
  • X is a group that does not affect the formation of a singlet intermediate.
  • the photosensitive crosslinker loses N2 molecules under ultraviolet light to obtain a carbene intermediate containing an electrically neutral divalent carbon atom.
  • the singlet intermediate undergoes an insertion reaction with the carbon-hydrogen bond in the ligand on the surface of the quantum dot, so that the quantum dots are cross-linked with each other.
  • X can be any functional group under the condition that it does not affect the generation of the intermediate;
  • R1 is a group that can stabilize the singlet carbene intermediate in the air, and R1 is designed to be an electron-donating group (i.e., a group that exhibits a negative electric field to the outside, and the electron-donating group is a group that can increase the electron cloud density on the benzene ring when the substituent replaces the hydrogen on the benzene ring).
  • the introduction of R1 is used to inhibit the conversion of the carbene intermediate from the singlet state to the triplet state, and to improve the stability of the singlet intermediate to oxygen in the air, so that the ligands in the exposure process are fully cross-linked.
  • R1 contains one or more structures selected from the group consisting of alkylamino, alkoxy, ether, acyloxy, amide, alkyl, alkylene, carboxymethyl, and phenyl; n is 2, 3, or 4; and X is selected from the group consisting of H, halogen, hydroxyl, alkyl and its derivatives, alkoxy and its derivatives, amino, and nitrile.
  • X is selected from -Cl, -F, -OH, -H, -CH 3 , -CF 3 , -OCH 3 , -NH 2 or -CN, preferably -CF 3 , which is beneficial to improve the reaction activity.
  • R 1 contains one or more structures of phenyl, ether, and alkylene; n is 2, 3 or 4; and X is selected from -CF 3 .
  • the photosensitive crosslinker has 1-100 carbon atoms and a molecular weight of 100-10000; in view of molecular safety and ease of synthesis, the molecular weight is more preferably 500-2000.
  • the photosensitive crosslinking agent is selected from
  • the material of the quantum dots (material of single-component quantum dots,
  • the core or shell material of the core-shell quantum dots includes one or a combination of two or more of II-VI compounds, III-V compounds, IV-VI compounds, I-III-VI compounds, and perovskite nanocrystals.
  • the quantum dots are quantum dots with a core-shell structure.
  • the II-VI group compound includes one or a combination of two or more of CdSe , CdS, CdTe, CdxSes1 -xS , CdxSes1 -xTe , ZnO, ZnSe , ZnS, ZnTe , ZnxSes1 - xS , ZnxSes1 - xTe, CdxZn1 - xSe, CdxZn1-xS, CdxZn1 - xTe, HgSe, HgS , HgTe, HgxCd1 - xSe, HgxCd1 - xS, and HgxCd1- xTe, wherein 0 ⁇ x ⁇ 1.
  • the III-V group compound includes one or a combination of two or more of InP, InAs, InSb, InN, GaP, GaAs, GaSb, GaN, AlP, AlAs, AlSb, and AlN.
  • the IV-VI group compound includes one or a combination of two or more of PbS, PbSe, PbTe, PbxS1 -xS , PbxS1 -xTe , SnS, SnSe , SnTe, SnxS1 - xS, SnxS1- xTe, wherein 0 ⁇ x ⁇ 1.
  • the Group I-III-VI compound includes one or a combination of two or more of CuInS 2 , CuInSe 2 , and AgInS 2 .
  • the perovskite nanocrystals include one or a combination of two or more of CsPbY 3 , CH 3 NH 3 PbY 3 , FAPbY 3 , MAPbY 3 , wherein Y is selected from Cl, Br or I, and MA and FA represent methylammonium and formamide, respectively.
  • the number of carbon atoms of the surface ligands of the quantum dots is 3-30.
  • the surface ligands of the quantum dots contain hydrocarbon chains.
  • the main chain of the surface ligand of the quantum dot contains a carbon-hydrogen bond.
  • the surface ligands of the quantum dots contain one or more structures of thiol, carboxylic acid, amine, phosphine, and phosphonic acid.
  • the surface ligands of the quantum dots include one or a combination of two or more of oleylamine, oleic acid, octadecylamine, 1-dodecanethiol, trioctylphosphine, and octadecylphosphonic acid.
  • step (1) quantum dots and a photosensitive crosslinker are mixed in a solvent to obtain a solution, and the solution is formed into a thin layer; wherein the concentration of quantum dots in the solution is 5-1000 mg/ml, and the mass concentration ratio of quantum dots to the added photosensitive crosslinker is 1:(0.01-1).
  • the solvent of the solution is selected from one or a combination of two or more of toluene, chlorobenzene, n-hexane, n-octane, n-heptane, cyclohexane, dichloromethane, chloroform and tetrahydrofuran.
  • the molar absorption of the photosensitive crosslinking agent at the exposure treatment wavelength is The optical coefficient is 10 cm -1 M -1 to 10 6 cm -1 M -1 .
  • each step of the quantum dot thin film patterning method is implemented in air, nitrogen, argon or other inert gases.
  • the wavelength of the exposure treatment is 100-500 nm (more preferably 200-500 nm), and the light dose is 1-5000 mJ/cm 2 .
  • an elution solvent is used to remove the raw material that has not undergone cross-linking (remove the unexposed quantum dot area), and the elution solvent is a non-polar solvent (dielectric constant is less than 10), more preferably including one or a combination of more than two of toluene, chlorobenzene, n-hexane, n-octane, n-heptane, cyclohexane, dichloromethane, chloroform, and tetrahydrofuran.
  • a non-polar solvent dielectric constant is less than 10
  • the above method comprises the following specific steps:
  • the present invention also provides a patterned quantum dot film prepared by the above-mentioned quantum dot film patterning method.
  • the present invention also provides a photoelectric device, whose structural composition includes an anode, a cathode, and a quantum dot light-emitting layer, wherein the quantum dot light-emitting layer is the above-mentioned patterned quantum dot film or is prepared by the above-mentioned quantum dot film patterning method.
  • the quantum dot light-emitting layer is located between the cathode and the anode, and the materials of the anode and the cathode are independently selected from metals or carbon materials; the metal is selected from one or a combination of two or more of Al, Ag, Au, Cu, Mo, Mg, Ba, and Ca, and the carbon material is selected from one or a combination of two or more of carbon nanotubes, graphite, graphene, and carbon fibers.
  • the structure of the optoelectronic device further comprises an electron injection layer, a hole injection layer, an electron transport layer and a hole transport layer, wherein the electron injection layer and the electron transport layer are located between the cathode and the quantum dot light-emitting layer, the electron injection layer is close to the cathode side, and the electron transport layer is close to the quantum dot light-emitting layer; the hole injection layer and the hole transport layer are located between the anode and the quantum dot light-emitting layer, the hole injection layer is close to the anode side, and the hole transport layer is close to the quantum dot light-emitting layer side.
  • the material of the electron injection layer includes one or a combination of two or more of alkali metal halides, alkali metal organic complexes, organic phosphorus oxides, and organic thio (or seleno) phosphine compounds.
  • the material of the electron transport layer comprises a single metal oxide and/or a doped metal oxide
  • the single metal oxide is selected from ZnO, ZrO 2 , SnO 2 , BaO, TiO 2 , Ta 2 O 3
  • the doped metal oxide is the above-mentioned single metal oxide doped with a certain proportion of one or more elements selected from Al, Li, Ga, Mg, Sn, In, F, Cl, etc.
  • the material of the hole injection layer is selected from poly(3,4-ethylenedioxythiophene), poly(styrenesulfonic acid), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4'-tris(2-naphthylphenylamino)triphenylamine, 1,4,5,8,9,12-hexaazatriphenyl-2,3,6,7,10,11-hexanitrile, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, metal oxides such as NiO, MoO 2 , WO 3 , CrO 3 , CuO, and transition metal sulfur compounds such as MoS 2 , MoSe 2 , WS 2 , CuS, WS 2 , etc., or a combination of two or more thereof.
  • metal oxides such as NiO, MoO 2 , WO
  • the material of the hole transport layer is selected from poly (3-hexylthiophene-2,5-diyl), poly (9-vinylcarbazole), poly [[(2,4-dimethylphenyl) imino] -1,4-phenylene (9,9-dioctyl-9H-fluorene-2,7-diyl) -1,4-phenylene], poly (9,9-dioctylfluorene-2,7-diyl), poly [bis (4-phenyl) (4-butylphenyl) amine], poly [(9,9-dioctylfluorenyl-2,7-diyl) -co -(4,4'-(N-(4-tert-butylphenyl)diphenylamine)], poly[9,9-dioctylfluorene-bis-N,N-(4-butylphen
  • the above-mentioned optoelectronic device is an array optoelectronic device.
  • the present invention provides a quantum dot patterning method that can be implemented in air and does not damage the photoelectric properties of quantum dots through the chemical design of cross-linked molecules. Electron-donating groups are introduced into carbene cross-linked molecules to make the energy of singlet carbene intermediates significantly lower than that of triplet states. In air, singlet carbene does not convert to triplet states to react with oxygen, but can realize quantum dot film patterning by cross-linking quantum dot surface ligands.
  • the present invention has the following beneficial effects:
  • This method is not only feasible in an inert gas atmosphere such as nitrogen and argon, but can also achieve efficient patterning of quantum dot materials of different types and compositions in air.
  • the resulting pattern resolution can reach 2 microns, which is close to the limit resolution of the UV lithography machine used.
  • the operation is simple and easy, and is suitable for low-cost, large-scale actual production and application;
  • the method for constructing the light-emitting layer of the quantum dot light-emitting display device provided by the present invention can be applied to actual QLEDs (quantum dot light-emitting diodes), and exhibits a level comparable to that of ordinary thin-film devices in terms of luminous brightness and current density, and can maintain the electrical properties of the quantum dot material itself.
  • the efficient and stable patterning method in the air has opened up an important path for the development of full-color light-emitting displays based on quantum dots.
  • FIG1 is a diagram showing the cross-linking mechanism of quantum dots and carbene cross-linkers
  • FIG2 is a schematic diagram of the process of patterning a quantum dot film
  • FIG3 is an optical photograph of three cadmium-free quantum dot patterns with different luminescent colors based on the photosensitive crosslinker A in Example 1 under a fluorescence microscope;
  • FIG4 is an optical photograph of a ZnSe/ZnS quantum dot pattern with different ligands under a fluorescence microscope based on a photosensitive crosslinker A in Example 2;
  • FIG5 is an optical photograph of a lnP/ZnS quantum dot pattern under a fluorescence microscope based on the photosensitive crosslinker B in Example 3;
  • FIG6 is an optical photograph of a lnP/ZnS quantum dot pattern under a fluorescence microscope based on the photosensitive crosslinker C in Example 4;
  • FIG7 is an optical photograph of three cadmium-based quantum dot patterns with different luminescent colors under a fluorescence microscope based on the photosensitive crosslinker A in Example 5;
  • FIG8 is an optical photograph of a cadmium-based CdSe/Cd1 -xZnxSe / ZnSe quantum dot pattern under a fluorescence microscope based on photosensitive crosslinkers B and C in Example 6;
  • FIG9 is an optical photograph of three quantum dot multicolor patterns in Example 7 under a fluorescence microscope
  • FIG10 is a graph showing the molar absorption coefficients of three photosensitive crosslinking agents A, B, and C;
  • FIG11 is a graph showing the change in fluorescence quantum yield of two different color lnP/ZnS quantum dot films before and after patterning
  • FIG12 is a graph showing the fluorescence lifetime change of a lnP/ZnS quantum dot film before and after patterning
  • FIG13 is a graph showing the change in fluorescence quantum yield of a cadmium-based CdSe/Cd1 -xZnxSe / ZnSe quantum dot film before and after patterning;
  • FIG14 is a diagram of the constructed cadmium-based and InP-based QLEDs devices, wherein A is a diagram of the specific structure of cadmium-based and InP-based QLEDs, B is a photograph of the electroluminescent pattern of cadmium-based QLEDs, C is a diagram of the relationship between current density and luminous brightness and voltage of cadmium-based QLEDs, D is a diagram of the luminous wavelength of cadmium-based QLEDs at different voltages and a diagram of the unit pixel of the QLEDs actually lit up in the test, E is a diagram of the relationship between current density and luminous brightness and voltage of InP-based QLEDs, and F is a diagram of the luminous wavelength of InP-based QLEDs at different voltages;
  • FIG15 is a graph showing the change in fluorescence quantum yield of a lnP/ZnS quantum dot film before and after patterning
  • FIG16 is a graph showing the fluorescence lifetime change of a lnP/ZnS quantum dot film before and after patterning
  • FIG17 is a photo of the effect of InP/ZnS quantum dot patterning under a fluorescence microscope
  • FIG. 18 is a photograph showing the effect of InP/ZnS quantum dot patterning under a fluorescence microscope.
  • This preparation example provides a photosensitive crosslinker molecule A, and its synthesis method is as follows (refer to patent PCT/CA2022/050293):
  • the colored mixture was filtered and washed with a dichloromethane solution, and purified by silica gel column chromatography using hexane and dichloromethane as eluents to obtain a yellow oily photosensitive crosslinker A.
  • This preparation example provides a photosensitive crosslinker molecule B, and its synthesis method is as follows (refer to patent PCT/CA2022/050293):
  • This preparation example provides a photosensitive crosslinker molecule C, and its synthesis method is as follows (refer to the literature "Stefania F. Musolino, et al. Structure–function relationships in aryl diazirines reveal optimal design features to maximize C–H insertion, Chem. Sci., 2021, 12, 12138–12148”):
  • Triethylamine (6.8 mL) and iodine (4.52 g) were added to a dichloromethane solution (41 mL) of 1,8-bis(4-(3-(trifluoromethyl)diazetidine-3-yl)phenoxy)octane (4.2 g) at 0°C.
  • the colored mixture was stirred at 0°C for 1 hour, diluted with a dichloromethane solution, and washed with a saturated aqueous sodium thiosulfate solution.
  • the organic extract was washed with brine after extraction with a dichloromethane solution three times, dried with magnesium sulfate, filtered and concentrated, and the product was purified by silica gel column chromatography using pentane and ether as eluents to obtain a light yellow solid photosensitive crosslinker C.
  • This preparation example provides a photosensitive crosslinker molecule D, and its synthesis method is as follows (refer to patent PCT/CA2022/050293):
  • This embodiment provides a quantum dot patterning method based on a photosensitive crosslinker molecule A and three cadmium-free quantum dot patterned films; wherein the quantum dots used for patterning include red and green lnP (core) / ZnS (shell) quantum dots, and the surface ligands are mainly oleic acid.
  • the synthesis references of red and green quantum dots (Bing Chen, et al. InP Quantum Dots: Synthesis and Lighting Applications, Small, 2020, 16, 2002454); including ZnSe (core) / ZnS (shell) blue quantum dots, the surface ligands are mainly oleylamine and oleic acid, and the synthesis references of blue quantum dots (Min Gao, et al. Bulk-like ZnSe Quantum Dots Enabling Efficient Ultra-narrow Blue Light-Emitting Diodes, Nano Lett., 2021, 21, 7252-7260).
  • the specific implementation steps are as follows:
  • red quantum dots the concentration of lnP/ZnS red quantum dots in the solution is 30 mg/mL, and the concentration of photosensitive crosslinker A is 1 mg/mL; for green quantum dots, the concentration of lnP/ZnS green quantum dots in the solution is 30 mg/mL, and the concentration of photosensitive crosslinker A is 2 mg/mL; for blue quantum dots, the concentration of ZnSe/ZnS blue quantum dots in the solution is 20 mg/mL, and the concentration of photosensitive crosslinker A is 1 mg/mL;
  • the photosensitive crosslinker A in the exposed part crosslinks with the oleylamine or oleic acid ligand on the surface of the quantum dots, changing the solubility of the quantum dots in toluene, which is different from the unexposed part;
  • FIG1 The cross-linking mechanism of quantum dots and carbene cross-linking agents in the quantum dot patterning method of the present invention is shown in FIG1 , and the process of quantum dot film patterning is shown in FIG2 .
  • FIG3 The optical microscope photos of the red, green and blue patterns prepared in this embodiment are shown in FIG3 , where A is a red quantum dot circular array pattern with a diameter of 30 ⁇ m; B is an "animal dog” pattern formed by green quantum dots; and C is a "Tsinghua University emblem” pattern formed by blue quantum dots, showing that the method can construct Complex pattern capabilities.
  • This embodiment provides a quantum dot patterning method based on a photosensitive crosslinker A and a patterned film of quantum dots with different ligands.
  • the quantum dots used in this embodiment are ZnSe/ZnS blue quantum dots, and the surface ligands are mainly 1-dodecanethiol.
  • the preparation method of quantum dots is based on the literature Jeehye Yang, et al. Nondestructive Photopatterning of Heavy-Metal-Free Quantum Dots, Adv. Mater., 2022, 34, 2205504.
  • Example 2 Compared with the preparation method of the blue ZnSe/ZnS quantum dot patterned film in Example 1, the difference between this embodiment and Example 1 is that the surface ligands oleylamine and oleic acid of the ZnSe/ZnS blue quantum dots are replaced with 1-dodecanethiol to obtain a blue quantum dot array with a line width of 2 microns as shown in Figure 4.
  • This embodiment provides a quantum dot patterning method based on a photosensitive crosslinker B and a quantum dot patterned film.
  • the selected InP/ZnS red quantum dots are the same as those in Example 1, and the surface ligand is oleylamine or oleic acid.
  • the specific implementation steps are as follows:
  • a commercial silicon wafer was used as a substrate and ultrasonically cleaned for 15 minutes using organic solvents such as toluene, acetone, methanol, and isopropanol.
  • organic solvents such as toluene, acetone, methanol, and isopropanol.
  • a solution of red lnP/ZnS quantum dots and photosensitive crosslinker B was spin-coated on one side of the silicon wafer at a speed of 1500 rpm.
  • the solvent was toluene.
  • the concentration of the lnP/ZnS red quantum dots in the solution was 30 mg/mL, and the concentration of the photosensitive crosslinker B was 2 mg/mL.
  • the red quantum dot film was selectively exposed using a mask.
  • the exposure light source was 365 nm
  • the light dose was 200 mJ/cm 2
  • the illumination time was 20 s.
  • the photosensitive crosslinker B in the exposed part cross-linked with the ligands on the surface of the quantum dots, which changed the solubility of the red quantum dots in toluene and distinguished it from the unexposed part.
  • the quantum dot film is immersed in toluene, and the quantum dots in the unexposed part fall off the silicon wafer.
  • the selectively exposed part shows a red quantum dot diamond array pattern as shown in FIG. 5 , with a diamond side length of 50 ⁇ m.
  • This embodiment provides a quantum dot patterning method based on a photosensitive crosslinker C and a quantum dot patterned film.
  • the same InP/ZnS red quantum dots as in Example 1 are selected.
  • the specific implementation steps are as follows:
  • a commercial silicon wafer was used as a substrate and ultrasonically cleaned for 15 minutes using organic solvents such as toluene, acetone, methanol, and isopropanol.
  • organic solvents such as toluene, acetone, methanol, and isopropanol.
  • a solution of red lnP/ZnS quantum dots and photosensitive crosslinker C was spin-coated on one side of the silicon wafer at a speed of 1500 rpm.
  • the solvent was toluene.
  • the concentration of the lnP/ZnS red quantum dots in the solution was 30 mg/mL, and the concentration of the photosensitive crosslinker C was 2 mg/mL.
  • the red quantum dot film is selectively exposed using a mask in an air atmosphere with an exposure light source of 365nm, light dose of 300mJ/cm 2 , light exposure time of 30s, the photosensitive crosslinker C in the exposed part crosslinks with the ligands on the surface of the quantum dots, changing the solubility of the red quantum dots in toluene, which is different from the unexposed part;
  • the quantum dot film is immersed in toluene, and the quantum dots in the unexposed part fall off the silicon wafer.
  • the selectively exposed part shows a red quantum dot square array pattern as shown in FIG. 6 , where the side length of the square is 60 ⁇ m.
  • This embodiment provides a quantum dot patterning method based on a photosensitive crosslinker A and a patterned film of three cadmium-based quantum dots.
  • Cadmium-based red quantum dots CdSe/CdS are selected, the surface ligand is oleylamine, and the preparation method is referenced to the literature (Chaodan Pu, et al. Electrochemically-stable ligands bridge the photoluminescence-electroluminescence gap of quantum dots. Nat.
  • the cadmium-based green quantum dots CdSe/Cd 1-x Zn x Se 1-y S y /ZnS are selected, the surface ligand is oleic acid, and the quantum dot preparation method is referenced to the literature (Himchan Cho, et al. Direct Optical Patterning of Quantum Dot Light-Emitting Diodes via In Situ Ligand Exchange. Adv. Mater., 2020, 32, 2003805), and the cadmium-based blue quantum dots Cd 1-x Zn x S/ZnS are selected, and the surface ligand is oleic acid.
  • the method for preparing quantum dots is referred to the literature (Wan Ki Bae, et al.
  • a commercial silicon wafer was used as a substrate, and ultrasonically cleaned for 15 minutes using organic solvents such as toluene, acetone, methanol, and isopropanol; a solution of cadmium-based quantum dots and photosensitive crosslinker A was spin-coated on one side of the silicon wafer at a speed of 1500 rpm, and the solvent was toluene.
  • organic solvents such as toluene, acetone, methanol, and isopropanol
  • a solution of cadmium-based quantum dots and photosensitive crosslinker A was spin-coated on one side of the silicon wafer at a speed of 1500 rpm, and the solvent was toluene.
  • red quantum dots the concentration of CdSe/CdS red quantum dots in the solution was 30 mg/mL, and the concentration of photosensitive crosslinker A was 1 mg/mL; for green quantum dots, the concentration of CdSe/Cd 1-x Zn x Se 1-y S y /ZnS quantum dots in the solution was 30 mg/mL, and the concentration of photosensitive crosslinker A was 2 mg/mL; for blue quantum dots, the concentration of Cd 1-x Zn x S/ZnS blue quantum dots in the solution was 20 mg/mL, and the concentration of photosensitive crosslinker A was 1 mg/mL;
  • the photosensitive crosslinker A in the exposed part crosslinks with the ligands on the surface of the quantum dots, changing the solubility of the quantum dots in toluene, which is different from the unexposed part;
  • the quantum dot film is immersed in toluene, and the quantum dots in the unexposed part fall off the silicon wafer, and the selectively exposed part shows the pattern shown in FIG7 .
  • a to C in FIG7 are red, green, and blue patterns, respectively;
  • This embodiment provides a quantum dot patterning method based on photosensitive crosslinkers B and C and a cadmium-based quantum dot patterned film.
  • FIG8 is a red quantum dot array with a line width of 50 microns obtained based on photosensitive crosslinker B.
  • the concentration of quantum dots in the solution is 30 mg/mL
  • the concentration of photosensitive crosslinker B is 1 mg/mL
  • the light dose is 200 mJ/cm 2
  • B in FIG8 is a red quantum dot array with a line width of 10 microns obtained based on photosensitive crosslinker C.
  • the concentration of quantum dots in the solution is 30 mg/mL
  • the concentration of photosensitive crosslinker C is 1 mg/mL
  • the light dose is 300 mJ/cm 2 .
  • This embodiment provides a quantum dot patterning method based on photosensitive crosslinker A and a multicolor patterned film of three-color quantum dots.
  • the selected red, green, and blue quantum dots are the same as those in Example 1.
  • the specific implementation steps are as follows:
  • a commercial silicon wafer was used as a substrate and ultrasonically cleaned for 15 minutes using organic solvents such as toluene, acetone, methanol, and isopropanol; a solution of red lnP/ZnS quantum dots and photosensitive crosslinker A was first spin-coated on one side of the silicon wafer at a speed of 1500 rpm, wherein the solvent was toluene, the concentration of the lnP/ZnS red quantum dots in the solution was 30 mg/mL, and the concentration of the photosensitive crosslinker A was 1 mg/mL;
  • the quantum dot film is immersed in toluene, and the unexposed blue quantum dots fall off the silicon wafer, while the selectively exposed blue portions appear and are arranged in parallel and staggered relation with the previously cross-linked red and green array patterns, as shown in FIG9 .
  • the size of a single array is 10 ⁇ m ⁇ 50 ⁇ m.
  • Test Example 1 Determination of the molar absorption coefficient of photosensitive cross-linking molecules
  • This test example provides molar absorption coefficient curves of three photosensitive crosslinkers A, B, and C, as shown in Figure 10.
  • the three photosensitive crosslinkers are respectively configured with solutions of about 6 ⁇ 10 -4 mol/L, and the solvent is toluene.
  • the corresponding ultraviolet absorbance A is tested using a Cary 5000 UV-Vis-NIR spectrometer.
  • This test example compares the fluorescence quantum yields of cadmium-free red and green quantum dots before and after patterning.
  • the samples were prepared in air, and the selected InP/ZnS red quantum dots and InP/ZnS green quantum dots were the same as those in Example 1.
  • the specific implementation steps are as follows:
  • a red quantum dot solution was spin-coated at a speed of 1500 rpm.
  • the solvent was toluene.
  • the concentration of lnP/ZnS red quantum dots in the solution was 30 mg/mL.
  • the fluorescence quantum yield of the film that had not undergone the patterning step was tested using a Horiba FluoroMax Plus spectrometer.
  • step (3) The film prepared according to the method of step (2) was subjected to ultraviolet exposure, with an illumination wavelength of 365 nm, an illumination dose of 200 mJ/cm 2 , and an illumination time of 20 s, and the fluorescence quantum yield of the film after the exposure step was measured using a Horiba FluoroMax Plus spectrometer;
  • the luminescence quantum yield of the film after each patterning step was tested.
  • the concentration of green quantum dots in the spin coating solution was 30 mg/mL
  • the concentration of photosensitive crosslinker A was 2 mg/mL
  • the illumination wavelength was 365 nm
  • the illumination dose was 200 mJ/cm 2
  • the illumination time was 20 s.
  • Test Example 3 Changes in fluorescence lifetime before and after quantum dot patterning
  • This test example examines the change in fluorescence lifetime before and after quantum dot patterning, prepares samples in air, and selects the InP/ZnS red quantum dots in Example 1.
  • the specific implementation steps are as follows:
  • a 2 cm ⁇ 2 cm quartz sheet was selected as the substrate, and a lnP/ZnS red quantum dot solution was spin-coated at a speed of 1500 rpm.
  • the solvent was toluene, and the concentration of lnP/ZnS red quantum dots in the solution was 30 mg/mL.
  • the average fluorescence lifetime of the film that had not undergone the patterning step was tested using the Horiba FluoroMax Plus with time-correlated single photon counting (TCSPC) system.
  • step (3) subjecting the film obtained in step (2) to ultraviolet exposure, with an illumination wavelength of 365 nm, an illumination dose of 200 mJ/cm 2 , and an illumination time of 20 s, and using a Horiba FluoroMax Plus with time-correlated single photon counting (TCSPC) system to test the average fluorescence lifetime of the film after the exposure step;
  • TCSPC time-correlated single photon counting
  • the average fluorescence lifetime of the initial film without quantum dots is 31.12ns. After mixing to form a quantum dot and photosensitive crosslinker film, the average fluorescence lifetime is 31.00ns. After UV exposure, the average fluorescence lifetime of the film is 28.98ns. After elution, the average fluorescence lifetime of the film is 30.59ns.
  • the fluorescence quantum yield of a cadmium-based quantum dot before and after patterning is compared.
  • the results are shown in Figure 13.
  • the quantum dots are the red CdSe/Cd1 -xZnxSe / ZnSe quantum dots in Example 6.
  • the specific implementation steps are the same as the red InP/ZnS quantum dots in Test Example 2.
  • the red CdSe/ Cd1- xZnxSe /ZnSe quantum dots have a fluorescence yield retention of 80% compared to the initial film.
  • Test Example 5 Construction of patterned cadmium-based QLEDs light-emitting display device and evaluation of corresponding electrical properties
  • This test example provides a construction of a patterned cadmium-based QLEDs light-emitting display device and the corresponding electrical performance evaluation.
  • the CdSe/Cd1 - xZnxSe /ZnSe red quantum dots in Example 6 are selected, and the light-emitting display device refers to the ITO/poly(3,4-ethylenedioxythiophene) provided in the literature Chaoyu Xiang, et al. High efficiency and stability of ink-jet printed quantum dot light emitting diodes.
  • the cleaned ITO substrate was surface treated with plasma for 6 min; then fixed on a spin coater, spin coated with PEDOT:PSS solution at a speed of 4000 rpm for 40 s, and heated and annealed at 150°C for 15 min;
  • a quantum dot layer (QDs) was continuously constructed on the above substrate.
  • a mixed solution of red quantum dots and photosensitive crosslinker A was prepared.
  • the solvent was chlorobenzene.
  • the concentration of CdSe/Cd1 -xZnxSe / ZnSe red quantum dots in the solution was 10 mg/mL, and the concentration of photosensitive crosslinker A was 1 mg/mL.
  • the solution was spin-coated at 2000 rpm for 60 s.
  • the film was then selectively irradiated with 365 nm ultraviolet light using a mask.
  • the irradiation dose was 300 mJ/ cm2 to fully crosslink the ligands on the surface of the quantum dots.
  • the area where no crosslinking reaction occurred was dynamically eluted using chlorobenzene solvent (50-100 ⁇ L of chlorobenzene was dripped on the top of the film at 2000 rpm) to obtain a patterned film.
  • the film was heated and annealed at 80°C for 10 min.
  • the difference in the construction of the light-emitting layer was that no mask was used.
  • the entire film was irradiated to avoid the influence of excessive leakage current, thereby better reflecting the influence of this crosslinking patterning method on the photoelectric performance of the device.
  • ZnO ethanol solution was spin coated at 2000 rpm for 40 s and heated and annealed at 80 °C for 20 min;
  • the electrical performance of the device was evaluated.
  • the device was encapsulated with ultraviolet curing resin.
  • the device parameters and performance such as QLED brightness, current density and emission wavelength were tested in an air atmosphere using a combination of a QE-PRO spectrometer and a Keithley 2400.
  • Figure 14C shows the current density and emission brightness of the constructed patterned red QLED device versus voltage; the current density is about 700mA/ cm2 , and the emission brightness reaches 12000cd/ m2 ;
  • Figure 14D shows the emission wavelength of the patterned QLEDs at different voltages of 2, 3, 4, and 5V, all at 620nm.
  • the square pixel of the QLEDs that was actually lit in the test has an area of 7.25mm2 .
  • Test Example 6 Construction of InP-based QLEDs light-emitting display devices and evaluation of their electrical properties
  • This test example provides a construction of a patterned InP-based-QLEDs light-emitting display device and the corresponding electrical performance evaluation.
  • the InP/ZnS red quantum dots in Example 1 are selected, and the structure of the light-emitting display device is the same as that in Test Example 5.
  • the cleaned ITO substrate was surface treated with plasma for 20 min; then fixed on a spin coater, spin coated with PEDOT:PSS solution at 3000 rpm for 30 s, and heated and annealed at 150°C for 15 min;
  • QDs quantum dot layer
  • the solvent is octane
  • the concentration of red quantum dots in the solution is 20 mg/mL
  • the concentration of photosensitive crosslinker A is 1 mg/mL
  • spin coating is performed at 2000 rpm for 60 s
  • the entire film is cross-linked by 365 nm ultraviolet light
  • the light dose is 100 mJ/cm 2
  • dynamically eluted using octane solvent and heated annealed at 80°C for 10 min;
  • ZnO ethanol solution was spin coated at 2000 rpm for 40 s and heated and annealed at 80 °C for 20 min;
  • FIG. 14E is a graph of the current density and emission brightness of the constructed patterned red InP-based QLED device versus voltage; the current density is about 600mA/ cm2 , and the emission brightness reaches 35000cd/ m2 ;
  • Figure 14F is the emission wavelength of the patterned QLEDs at different voltages of 2, 3, 4, and 5V, all at 620nm.
  • Test Example 7 Changes in fluorescence quantum yield before and after patterning
  • This test example investigates the change in fluorescence quantum yield of a quantum dot before and after patterning under the action of a photosensitive crosslinker.
  • the photosensitive crosslinker A is changed to C, and the patterning conditions are changed to the concentration of lnP/ZnS red quantum dots in the solution is 30 mg/mL, the concentration of photosensitive crosslinker C is 2 mg/mL, the light dose is 300 mJ/ cm2 , and the light exposure time is 30 s.
  • the results are shown in Figure 15.
  • the quantum yield of the untreated initial film of the quantum dots is normalized to 100%. After patterning with photosensitive crosslinker C in air, the red lnP/ZnS quantum dots have a good yield retention of 80%.
  • Test Example 8 Changes in fluorescence lifetime before and after patterning
  • This test example investigates the change in fluorescence lifetime of a quantum dot before and after patterning under the action of a photosensitive crosslinker.
  • the photosensitive crosslinker A is changed to C
  • the patterning conditions are changed to the concentration of lnP/ZnS red quantum dots in the solution is 30 mg/mL
  • the concentration of photosensitive crosslinker C is 2 mg/mL
  • the light dose is 300 mJ/cm 2 .
  • the illumination time is 30s.
  • the results are shown in Figure 16.
  • the patterning step does not reduce the average fluorescence lifetime of the quantum dots themselves.
  • the average fluorescence lifetime of the initial film without quantum dots is 31.12ns
  • the average fluorescence lifetime of the final patterned film is 28.83ns.
  • This comparative example provides a method for preparing a patterned quantum dot film. Compared with the quantum dot patterning methods in Examples 1, 3, and 4, the difference in this comparative example is that the photosensitive crosslinker is replaced by 3,3'-(4,4'-perfluorobutane-1,4-diyl)bis(4,1-phenylene)bis(3-trifluoromethyl)-3H-diacridine from the provided A, B, and C, and the molecular formula is as follows:
  • the molecular synthesis method refers to the existing literature "Shaoyong Lu, et al. Beyond a Linker: The Role of Photochemistry of Crosslinkers in the Direct Optical Patterning of Colloidal Nanocrystals. Angew. Chem. Int. Ed., 2022, 61, e202202633", and the preparation method includes the following steps:
  • a triethylamine solution (3.06 mL) was added dropwise to a dichloromethane solution (21 mL) of 3,3'-((perfluorobutane-1,4-diyl)bis(4,1-phenylene))bis(3-(trifluoromethyl)diaziridine) (2.1 g) over 10 minutes, and iodine (2.04 g) was added to the resulting mixture three times, and stirring was continued at 0°C for 2 hours.
  • the reaction mixture was diluted with dichloromethane (60 mL) and transferred to a separatory funnel, and the organic layer was washed with water, a saturated sodium thiosulfate solution, water and brine, and dried over sodium sulfate.
  • the organic layer was purified by silica gel column chromatography to obtain the desired bright white crystalline cross-linked molecule.
  • the A, B, and C molecules designed in the present invention inhibit the process of the intermediate singlet state to the triplet state due to the introduction of electron-donating groups. Even in the air, the singlet intermediate and the surface ligand can be efficiently cross-linked to achieve patterning of the quantum dot material.
  • This comparative example provides a patterning effect of quantum dots under the action of different photosensitive crosslinking agents.
  • photosensitive crosslinking agent C is used in air.
  • the difference is that the ultraviolet light dose is changed from 300 mJ/cm 2 was replaced with 50mJ/cm 2 , and a portion of the red lnP/ZnS quantum dot film after exposure was immersed in toluene, but no pattern was seen (as shown in FIG18 ).
  • the reason is that photosensitive crosslinker A has a large molar absorption coefficient at a wavelength of 365nm and has a higher ultraviolet light utilization rate.
  • the tridentate crosslinking sites in photosensitive crosslinker A also make the crosslinking reaction more efficient.

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Abstract

本发明提供了一种量子点薄膜图案化方法与应用。该量子点薄膜图案化方法包括以下步骤：(1)将量子点与光敏交联剂混合后形成一薄层；(2)对所述薄层进行图案化曝光处理，得到图案化的量子点薄膜；其中，所述量子点的表面具有含有碳氢键的配体；所述光敏交联剂具有式Ⅰ所示的结构，式Ⅰ中，R1为供电子基团；n≥2；X为不影响单线态中间体生成的基团。该量子点薄膜图案化方法能在空气中实现不同种类、组成的量子点的高效图案化，具有分辨率高、普适性强、适用于大规模工业化生产的优点，可用于制备量子点LEDs等光电器件，能较大程度维持量子点材料本身的光电性能。

Description

一种量子点薄膜图案化方法与应用 技术领域
本发明属于光电技术领域，具体涉及一种图案化量子点薄膜的制备方法和发光显示器件的构筑。
背景技术
量子点(Quantum dos,QDs)，即尺寸小于玻尔半径的半导体纳米晶体，常见尺寸在2-20nm，由无机半导体核和表面配体构成，具有明显的体积效应、表面效应、尺寸效应等特性，其发光波长可根据尺寸可控调节，发射半峰宽窄，色域广，同时相比于传统硅等半导体材料，量子点可形成稳定的胶体溶液，以溶液法构筑低成本、大面积、高效率的光电器件。
在光电器件领域，量子点通常以薄膜形式作为光电活性层，图案化方法可以实现微米尺度分辨率的量子点阵列构筑，在高清多彩的平板显示或照明、传感成像、光电刺激等领域具有更广泛的应用前景。常规的量子点薄膜图案化方法存在缺陷，例如光刻技术难以保证量子点和光刻胶的兼容性，喷墨打印技术实现的图案分辨率有限(＞50微米)，电子束或激光直写等技术对量子点本身光电性能存在损伤。
近些年，基于量子点表面化学的新型图案化方法可高效实现高分辨率(＜5微米)的图案化量子点薄膜。但是，目前报道的这类方法大部分是在惰性气体下实施，当在空气中进行量子点图案化时，可能会存在无法形成图案或者降低量子点薄膜的光电性能等问题。CN114839835A利用含有双吖丙啶基团的光敏交联分子(即卡宾交联分子)实现了量子点薄膜的图案化，在氮气环境下，该交联分子光照产生的单线态卡宾中间体与量子点表面配体中的碳氢键进行插入反应，从而将量子点交联而实现图案化，但是具有较高能量的单线态卡宾中间体(分子中电子净自旋S＝0)易转变为三线态(分子中电子净自旋S＝1)，暴露在空气中时，所产生的三线态卡宾与空气中的氧气迅速反应，这一副反应使单线态卡宾耗尽，不能将量子点交联形成图案。此外，图案化过程中空气环境对量子点光电性能的影响常被忽视，尤其是无镉等重金属组分的III-V族量子点，其光电性质更易受氧气等因素的影响。这些问题都制约着量子点薄膜图案化方法在大规模、低成本生产中的实际发展与应用。因此亟需开发出可在空气中实施且对量子点性能无损的量子点薄膜图案方法。
发明内容
为了解决上述问题，本发明的目的在于提供一种量子点薄膜图案化方法与应用，该量子点薄膜图案化方法能在空气中实现不同种类、组成的量子点的高效图案化，具有分辨率高、普适性强、适用于大规模工业化生产的优点。
为了达到上述目的，本发明提供了一种量子点薄膜图案化方法，其包括以下步骤：(1)将量子点与光敏交联剂混合后形成一薄层；(2)对所述薄层进行图案化曝光处理，得到图案化的量子点薄膜；其中，所述量子点的表面具有含有碳氢键的配体；所述光敏交联剂具有式Ⅰ所示的结构：
式Ⅰ中，R1为供电子基团；n≥2；X为不影响单线态中间体生成的基团。
在式Ⅰ中，光敏交联剂在紫外光照下，失去N2分子，得到含有电中性二价碳原子的卡宾中间体，在曝光过程中单线态中间体与量子点表面配体中的碳氢键发生插入反应，使得量子点之间相互交联。X在不影响中间体生成的条件下可以是任意官能团；R1为在空气中能稳定单线态卡宾中间体的基团，R1设计为供电子基团(即对外表现负电场的基团，供电子基团是当取代基取代苯环上的氢后，能使苯环上电子云密度升高的基团)，R1的引入用于抑制卡宾中间体从单线态向三线态转换，提高单线态中间体对空气中氧气的稳定性，以使所述曝光过程中的配体充分交联。
根据本发明的具体实施方案，优选地，式Ⅰ中，R1含有烷基氨基、烷氧基、醚基、酰氧基、酰胺基、烷基、亚烷基、羧基甲基、苯基中的一种或两种以上的结构；所述n为2、3或4；X选自H、卤素、羟基、烷基及其衍生物、烷氧基及其衍生物、氨基、腈基。
根据本发明的具体实施方案，优选地，X选自-Cl、-F、-OH、-H、-CH3、-CF3、-OCH3、-NH2或-CN，优选为-CF3，利于提高反应活性。
根据本发明的具体实施方案，优选地，R1含有苯基、醚基、亚烷基中的一种或两种以上的结构；n为2、3或4；X选自-CF3。
根据本发明的具体实施方案，优选地，所述光敏交联剂的碳原子数为1-100，分子量为100-10000；从分子安全性和合成简易性考虑，分子量更优选为500-2000。
根据本发明的具体实施方案，优选地，所述光敏交联剂选自
(1,3,5-tris((2-(3-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)ethoxy)methyl)benzene，光敏交联剂A)、
(3-(trifluoromethyl)-3-(3-(2-((4-((2-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)ethoxy)methyl)benzyl)oxy)ethoxy)phenyl)-3H-diazirine，光敏交联剂B)、
(bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)octane，光敏交联剂C)、
(1,2,4,5-tetrakis((2-(3-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)ethoxy)methyl)benzene，光敏交联剂D)中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述量子点的材料(单一组分量子点的材料、 核壳量子点的核或壳的材料)包括II-VI族化合物、III-V族化合物、IV-VI族化合物、I-III-VI族化合物、钙钛矿纳米晶体中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述量子点为核壳结构的量子点。
根据本发明的具体实施方案，优选地，所述II-VI族化合物包括CdSe、CdS、CdTe、CdxSe1-xS、CdxSe1-xTe、ZnO、ZnSe、ZnS、ZnTe、ZnxSe1-xS、ZnxSe1-xTe、CdxZn1-xSe、CdxZn1-xS、CdxZn1-xTe、HgSe、HgS、HgTe、HgxCd1-xSe、HgxCd1-xS、HgxCd1-xTe中的一种或两种以上的组合，其中，0＜x＜1。
根据本发明的具体实施方案，优选地，所述III-V族化合物包括lnP、InAs、InSb、InN、GaP、GaAs、GaSb、GaN、AlP、AlAs、AlSb、AlN中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述IV-VI族化合物包括PbS、PbSe、PbTe、PbxSe1-xS、PbxSe1-xTe、SnS、SnSe、SnTe、SnxSe1-xS、SnxSe1-xTe中的一种或两种以上的组合，其中，0＜x＜1。
根据本发明的具体实施方案，优选地，所述I-III-VI族化合物包括CuInS2、CuInSe2、AgInS2中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述钙钛矿纳米晶体包括CsPbY3、CH3NH3PbY3、FAPbY3、MAPbY3中的一种或两种以上的组合，其中，Y选自Cl、Br或I，MA和FA分别代表甲基铵和甲酰胺。
根据本发明的具体实施方案，优选地，所述量子点的表面配体的碳原子数为3-30。
根据本发明的具体实施方案，优选地，所述量子点的表面配体含有碳氢链。
根据本发明的具体实施方案，优选地，所述量子点的表面配体的主链含有碳氢键。
根据本发明的具体实施方案，优选地，所述量子点的表面配体含有硫醇、羧酸、胺、膦、膦酸中的一种或两种以上的结构。
根据本发明的具体实施方案，优选地，所述量子点的表面配体包括油胺、油酸、十八胺、1-十二烷硫醇、三辛基膦、十八烷基膦酸中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，步骤(1)中，将量子点与光敏交联剂混合于溶剂中得到溶液，将该溶液形成一薄层；其中，所述溶液中的量子点的浓度为5-1000mg/ml，量子点与添加的光敏交联剂的质量浓度比为1：(0.01-1)。
根据本发明的具体实施方案，优选地，所述溶液的溶剂选自甲苯、氯苯、正己烷、正辛烷、正庚烷、环己烷、二氯甲烷、氯仿、四氢呋喃中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述光敏交联剂在曝光处理波长下的摩尔吸 光系数为10cm-1M-1至106cm-1M-1。
根据本发明的具体实施方案，优选地，所述量子点薄膜图案化方法的各个步骤分别在空气、氮气、氩气或其他惰性气体中进行实施。
根据本发明的具体实施方案，优选地，步骤(2)中，所述曝光处理的波长为100-500nm(更优选为200-500nm)，光照剂量为1-5000mJ/cm2。
根据本发明的具体实施方案，优选地，在对所述薄层进行曝光处理后，采用洗脱溶剂去除未发生交联的原料(去除未曝光量子点区域)，所述洗脱溶剂为非极性溶剂(介电常数小于10)，更优选包括甲苯、氯苯、正己烷、正辛烷、正庚烷、环己烷、二氯甲烷、氯仿、四氢呋喃中的一种或两种以上的组合。
根据本发明的具体实施方案，上述方法包括以下具体步骤：
(1)在基底的一侧形成量子点与光敏交联剂均匀分散的薄膜层；
(2)对上述量子点薄膜层进行特定区域曝光处理，曝光部分发生配体交联反应；
(3)接着利用溶剂洗脱，去除未曝光的部分，从而获得图案化的量子点薄膜。
本发明还提供了上述量子点薄膜图案化方法制得的图案化的量子点薄膜。
本发明还提供了一种光电器件，其结构组成包含阳极、阴极、量子点发光层，其中，所述量子点发光层为上述图案化的量子点薄膜或者由上述量子点薄膜图案化方法制得。
根据本发明的具体实施方案，优选地，所述量子点发光层位于阴极与阳极之间，所述阳极和所述阴极的材料各自独立地选自金属或碳材料；所述金属选自Al、Ag、Au、Cu、Mo、Mg、Ba、Ca中的一种或两种以上的组合，所述碳材料选自碳纳米管、石墨、石墨烯、碳纤维中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述光电器件的结构组成还包含电子注入层、空穴注入层、电子传输层、空穴传输层，所述电子注入层和电子传输层位于阴极与所述量子点发光层之间，所述电子注入层靠近阴极的一侧，所述电子传输层靠近所述量子点发光层；所述空穴注入层和空穴传输层位于阳极和所述量子点发光层之间，所述空穴注入层靠近阳极的一侧，所述空穴传输层靠近所述量子点发光层的一侧。
根据本发明的具体实施方案，优选地，所述电子注入层的材料包括碱金属卤化物、碱金属有机络合物、有机氧化磷、有机硫代(或硒代)膦化合物中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述电子传输层的材料包括单一金属氧化物和/或掺杂金属氧化物，所述单一金属氧化物选自ZnO、ZrO2、SnO2、BaO、TiO2、Ta2O3 中的一种或两种以上的组合；所述掺杂金属氧化物为上述单一金属氧化物掺杂一定比例的Al、Li、Ga、Mg、Sn、In、F、Cl等中的一种或两种以上的元素。
根据本发明的具体实施方案，优选地，所述空穴注入层的材料选自聚(3,4-乙烯二氧基噻吩)、聚(苯乙烯磺酸)、4,4',4'-三(N-3-甲基苯基-N-苯基氨基)三苯胺、4,4',4'-三(2-萘基苯基氨基)三苯胺、1,4,5,8,9,12-六氮杂三苯-2,3,6,7,10,11-六腈、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌，NiO、MoO2、WO3、CrO3、CuO等金属氧化物、MoS2、MoSe2、WS2、CuS、WS2等过渡金属硫系化合物中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，所述空穴传输层的材料选自聚(3-己基噻吩-2,5-二基)、聚(9-乙烯咔唑)、聚[[(2,4-二甲基苯基)亚氨基]-1,4-亚苯基(9,9-二辛基-9H-芴-2,7-二基)-1,4-亚苯基]、聚(9,9-二辛基芴-2,7-二基)、聚[双(4-苯基)(4-丁基苯基)胺]、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(4-叔丁基苯基)二苯胺)]、聚[9,9-二辛基芴-双-N,N-(4-丁基苯基)-双-N,N-苯基-1,4-苯二胺]、三[4-(咔唑-9-基)苯基]胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺、聚(3,4-乙烯二氧基噻吩)、聚(苯乙烯磺酸)、石墨烯、NiO、WO3、CuI、CuSCN、CuO、CuInS2、GaN、C60、MoO3、V2O5、CrO3中的一种或两种以上的组合。
根据本发明的具体实施方案，优选地，上述光电器件为阵列式光电器件。
本发明通过交联分子的化学设计，提供一种可在空气中实施且无损量子点光电性质的量子点图案化方法，在卡宾交联分子中引入供电子基团，使单线态卡宾中间体的能量显著低于三线态，在空气中，单线态卡宾不转变为三线态与氧气反应，而可以通过交联量子点表面配体实现量子点薄膜图案化。本发明具有以下有益效果：
1、该方法不仅在氮气、氩气等惰性气体氛围中可行，在空气中也可以实现不同种类和组成的量子点材料的高效图案化，所得图案分辨率可达2微米，接近所采用的紫外光刻机的极限分辨率，操作简单易行，适用于低成本、大规模的实际生产与应用；
2、在空气条件下，设计的卡宾单线态中间体性质稳定，交联反应温和，对不同种类的量子点光学性质无损；
3、本发明提供的量子点发光显示器件发光层的构筑方法，可以应用在实际的QLEDs(量子点发光二极管)中，在发光亮度、电流密度等方面展现了与普通薄膜器件相当的水平，能保持量子点材料本身的电学性质，空气中高效稳定的图案化方法为开发基于量子点的全色发光显示器开辟了重要途径。
附图说明
图1为量子点与卡宾交联剂交联机理图；
图2为量子点薄膜图案化的流程示意图；
图3为实施例1中基于光敏交联剂A，三种不同发光颜色的无镉量子点图案在荧光显微镜下的光学照片；
图4为实施例2中基于光敏交联剂A，一种不同配体的ZnSe/ZnS量子点图案在荧光显微镜下的光学照片；
图5为实施例3中基于光敏交联剂B，一种lnP/ZnS量子点图案在荧光显微镜下的光学照片；
图6为实施例4中基于光敏交联剂C，一种lnP/ZnS量子点图案在荧光显微镜下的光学照片；
图7为实施例5中基于光敏交联剂A，三种不同发光颜色的镉基量子点图案在荧光显微镜下的光学照片；
图8为实施例6中基于光敏交联剂B、C，一种镉基CdSe/Cd1-xZnxSe/ZnSe量子点图案在荧光显微镜下的光学照片；
图9为实施例7中三种量子点多色图案在荧光显微镜下的光学照片；
图10为三种光敏交联剂A、B、C的摩尔吸光系数图；
图11为两种不同颜色lnP/ZnS量子点薄膜图案化前后荧光量子产率变化图；
图12为一种lnP/ZnS量子点薄膜图案化前后荧光寿命变化图；
图13为一种镉基CdSe/Cd1-xZnxSe/ZnSe量子点薄膜图案化前后荧光量子产率变化图；
图14为构筑的镉基和InP基QLEDs器件图，其中，A为镉基和InP基QLEDs具体结构图、B为镉基QLEDs电致发光图案照片、C为镉基QLEDs电流密度和发光亮度与电压关系图、D为镉基QLEDs不同电压下发光波长图和QLEDs实际测试点亮的单元像素图、E为InP基QLEDs电流密度和发光亮度与电压关系图、F为InP基QLEDs不同电压下发光波长图；
图15为一种lnP/ZnS量子点薄膜图案化前后荧光量子产率变化图；
图16为一种lnP/ZnS量子点薄膜图案化前后荧光寿命变化图；
图17为一种lnP/ZnS量子点图案化在荧光显微镜下的效果照片；
图18为一种lnP/ZnS量子点图案化在荧光显微镜下的效果照片。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
制备例1
本制备例提供一种光敏交联剂分子A，其合成方法如下(参照专利PCT/CA2022/050293)：
氩气气氛下，在无水四氢呋喃(10mL)中加入NaH(60％在矿物油中的分散体，632mg)，在0℃下逐滴加入2-(4-(3-(三氟甲基)-3H-二吖啶-3-基)苯氧基)乙烷-1-醇(3.26g)的四氢呋喃无水溶液(5mL)，搅拌反应10分钟。然后在0℃下滴加1,3,5-三(溴甲基)苯(1.52g)的无水四氢呋喃溶液(10mL)，并将反应物在室温下搅拌过夜。将有色混合物过滤处理，并用二氯甲烷溶液洗涤，使用己烷与二氯甲烷作为洗脱剂通过硅胶柱色谱法纯化，得到黄色油状的光敏交联剂A。
制备例2
本制备例提供一种光敏交联剂分子B，其合成方法如下(参照专利PCT/CA2022/050293)：
氩气气氛下，在无水四氢呋喃(30mL)中加入NaH(60％在矿物油中的分散体，1.68g)，在0℃下逐滴加入2-(4-(3-(三氟甲基)-3H-二吖啶-3-基)苯氧基)乙烷-1-醇(8.28g)的四氢呋喃无水溶液(15mL)，搅拌反应10分钟。然后在0℃下逐滴加入1,4-双(溴甲基)苯(4.44g)的无水四氢呋喃(20mL)，并将反应物在室温下搅拌过夜。将有色混合物过滤并用二氯甲烷洗涤，进一步通过硅胶柱色谱法纯化，使用戊烷与乙醚作为洗脱剂，得到光敏交联剂B。
制备例3
本制备例提供一种光敏交联剂分子C，其合成方法如下(参照文献“Stefania F.Musolino,et al.Structure–function relationships in aryl diazirines reveal optimal design features to maximize C–H insertion,Chem.Sci.,2021,12,12138–12148”)：
将三乙胺(6.8mL)和碘单质(4.52g)在0℃下依次加入1,8-双(4-(3-(三氟甲基)二氮杂环丁烷-3-基)苯氧基)辛烷(4.2g)的二氯甲烷溶液中(41mL)。将有色混合物在0℃下搅拌1小时，用二氯甲烷溶液稀释混合物，并用饱和硫代硫酸钠水溶液洗涤。用二氯甲烷溶液萃取3次后用盐水洗涤有机提取物，用硫酸镁干燥，过滤并浓缩，产物通过硅胶柱色谱法进行纯化，使用戊烷与乙醚作为洗脱剂，得到浅黄色固体光敏交联剂C。
制备例4
本制备例提供一种光敏交联剂分子D，其合成方法如下(参照专利PCT/CA2022/050293)：
氩气气氛下，在无水四氢呋喃(30mL)中加入NaH(60％在矿物油中的分散体，632mg)，在0℃下逐滴加入2-(4-(3-(三氟甲基)-3H-二吖啶-3-基)苯氧基)乙烷-1-醇(3.26g)的四氢呋喃无水溶液(15mL)，搅拌反应10分钟。然后在0℃下滴加1，2,4,5-四(溴甲基)苯的无水四氢呋喃溶液(20mL)，并将反应物在室温下搅拌过夜。将有色混合物过滤、洗涤处理，通过硅胶柱色谱法纯化得到黄色油状的光敏交联剂D。
实施例1
本实施例提供了基于光敏交联剂分子A的量子点图案化方法和三种无镉量子点的图案化薄膜；其中，图案化使用的量子点包括红色和绿色的lnP(核)/ZnS(壳)量子点，表面配体主要为油酸。红色和绿色量子点合成参考文献(Bing Chen,et al.InP Quantum Dots:Synthesis and Lighting Applications,Small,2020,16,2002454)；包括ZnSe(核)/ZnS(壳)蓝色量子点，表面配体主要为油胺与油酸，蓝色量子点合成参考文献(Min Gao,etal.Bulk-like ZnSe Quantum Dots Enabling Efficient Ultra-narrow Blue Light-Emitting Diodes,Nano Lett.,2021,21,7252-7260)。具体实施步骤如下：
(1)在空气氛围中，取硅片作为基底，使用有机溶剂甲苯、丙酮、甲醇与异丙醇分别超声清洗15min；在硅片一侧以1500rpm转速旋涂某一种颜色量子点和光敏交联剂A的溶液，溶剂为甲苯。对于红色量子点，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂A的浓度为1mg/mL；对于绿色量子点，溶液中lnP/ZnS绿色量子点的浓度为30mg/mL，光敏交联剂A的浓度为2mg/mL，对于蓝色量子点，溶液中ZnSe/ZnS蓝色量子点的浓度为20mg/mL，光敏交联剂A的浓度为1mg/mL；
(2)利用掩模版对一种颜色的量子点薄膜进行选择性曝光，曝光光源为365nm，光照剂量为50mJ/cm2，光照时间5s，曝光部分光敏交联剂A与量子点表面油胺或油酸配体交联，改变了量子点在甲苯中的溶解度，区别于未曝光部分；
(3)将上述量子点薄膜浸泡在甲苯中，未曝光部分量子点从硅片上脱落，选择性曝光的部分显现出图案。
本发明量子点图案化方法中量子点与卡宾交联剂交联机理如图1所示，量子点薄膜图案化的流程如图2所示。
本实施例分别制得的红色、绿色与蓝色图案的光学显微镜照片如图3所示，图3中A为红色量子点圆形阵列图案，圆形的直径为30微米；图3中B为绿色量子点形成的“动物狗”图案；图3中C为蓝色量子点形成的“清华校徽”图案，展现出本方法构筑 复杂图案的能力。
实施例2
本实施例提供了基于光敏交联剂A的量子点图案化方法和一种不同配体量子点的图案化薄膜。本实施例选用的量子点为ZnSe/ZnS蓝色量子点，表面配体主要为1-十二烷硫醇，量子点相关制备方法参照文献Jeehye Yang,et al.Nondestructive Photopatterning of Heavy-Metal-Free Quantum Dots,Adv.Mater.,2022,34,2205504。
相较于实施例1中蓝色ZnSe/ZnS量子点图案化薄膜的制备方法，本实施例与实施例1的区别在于：将ZnSe/ZnS蓝色量子点的表面配体油胺与油酸替换为1-十二烷硫醇，获得如图4所示的线宽为2微米的蓝色量子点阵列。
实施例3
本实施例提供了基于光敏交联剂B的量子点图案化方法和一种量子点的图案化薄膜。选用的lnP/ZnS红色量子点与实施例1中相同，表面配体为油胺或油酸。具体实施步骤如下：
(1)在空气氛围中，取商用硅片作为基底，使用有机溶剂甲苯、丙酮、甲醇与异丙醇分别超声清洗15分钟；在硅片一侧以1500rpm转速旋涂红色lnP/ZnS量子点和光敏交联剂B的溶液，溶剂为甲苯，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂B的浓度为2mg/mL；
(2)利用掩模版对红色量子点薄膜进行选择性曝光，在空气氛围中，曝光光源为365nm，光照剂量为200mJ/cm2，光照时间20s，曝光部分光敏交联剂B与量子点表面配体交联，改变了红色量子点在甲苯中的溶解度，区别于未曝光部分；
(3)将上述量子点薄膜浸泡在甲苯中，未曝光部分量子点从硅片上脱落，选择性曝光的部分显现出如图5所示的红色量子点菱形阵列图案，菱形边长为50微米。
实施例4
本实施例提供了基于光敏交联剂C的量子点图案化方法和一种量子点的图案化薄膜。选用与实施例1中相同的lnP/ZnS红色量子点。具体实施步骤如下：
(1)在空气氛围中，取商用硅片作为基底，使用有机溶剂甲苯、丙酮、甲醇与异丙醇分别超声清洗15分钟；在硅片一侧以1500rpm转速旋涂红色lnP/ZnS量子点和光敏交联剂C的溶液，溶剂为甲苯，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂C的浓度为2mg/mL；
(2)利用掩模版对红色量子点薄膜进行选择性曝光，在空气氛围中，曝光光源为 365nm，光照剂量为300mJ/cm2，光照时间30s，曝光部分光敏交联剂C与量子点表面配体交联，改变了红色量子点在甲苯中的溶解度，区别于未曝光部分；
(3)将上述量子点薄膜浸泡在甲苯中，未曝光部分量子点从硅片上脱落，选择性曝光的部分显现出如图6所示的红色量子点正方形阵列图案，正方形边长为60微米。
实施例5
本实施例提供了基于光敏交联剂A的量子点图案化方法和三种镉基量子点的图案化薄膜。选用镉基红色量子点CdSe/CdS，表面配体为油胺，制备方法参照文献(Chaodan Pu,et al.Electrochemically-stable ligands bridge the photoluminescence-electroluminescence gap of quantum dots.Nat.Commun.,2020,11(1):937)，选用的镉基绿色量子点CdSe/Cd1-xZnxSe1-ySy/ZnS，表面配体为油酸，该量子点制备方法参考文献(Himchan Cho,et al.Direct Optical Patterning of Quantum Dot Light-Emitting Diodes via In Situ Ligand Exchange.Adv.Mater.,2020,32,2003805)，选用的镉基蓝色量子点Cd1-xZnxS/ZnS，表面配体为油酸。量子点制备方法参考文献(Wan Ki Bae,et al.Gram-Scale One-Pot Synthesis of Highly Luminescent Blue Emitting Cd1-xZnxS/ZnS Nanocrystals.Chem.Mater.,2008,20,5307–5313)。具体实施步骤如下：
(1)在空气氛围中，取商用硅片作为基底，使用有机溶剂甲苯、丙酮、甲醇与异丙醇分别超声清洗15分钟；在硅片一侧以1500rpm转速旋涂镉基量子点和光敏交联剂A的溶液，溶剂为甲苯。对于红色量子点，溶液中CdSe/CdS红色量子点的浓度为30mg/mL，光敏交联剂A的浓度为1mg/mL；对于绿色量子点，溶液中CdSe/Cd1-xZnxSe1-ySy/ZnS量子点浓度为30mg/mL，光敏交联剂A的浓度为2mg/mL；对于蓝色量子点，溶液中Cd1-xZnxS/ZnS蓝色量子点的浓度为20mg/mL，光敏交联剂A的浓度为1mg/mL；
(2)利用掩模版对镉基量子点薄膜进行选择性曝光，在空气氛围中，曝光光源为365nm，光照剂量为50mJ/cm2，光照时间5s，曝光部分光敏交联剂A与量子点表面配体交联，改变了量子点在甲苯中的溶解度，区别于未曝光部分；
(3)将上述量子点薄膜浸泡在甲苯中，未曝光部分量子点从硅片上脱落，选择性曝光的部分显现出如图7所示的图案。图7中的A至C分别为红色、绿色、蓝色的图案；
实施例6
本实施例提供了基于光敏交联剂B和C的量子点图案化方法和一种镉基量子点的图案化薄膜。选用的CdSe/Cd1-xZnxSe/ZnSe红色量子点，配体主要为油酸，量子点制备 方法参考文献“Chaoyu Xiang,et al.High efficiency and stability of ink-jet printed quantum dot light emitting diodes.Nat Commun.,2020,11(1):1646”，具体的图案化实施步骤与实施例5相同，图案化效果图如图8所示，图8中A为基于光敏交联剂B获得的线宽为50微米的红色量子点阵列，实施过程中溶液中量子点的浓度为30mg/mL，光敏交联剂B的浓度为1mg/mL，光照剂量为200mJ/cm2，图8中B为基于光敏交联剂C获得的线宽为10微米的红色量子点阵列。实施过程中溶液中量子点的浓度为30mg/mL，光敏交联剂C的浓度为1mg/mL，光照剂量为300mJ/cm2。
实施例7
本实施例提供了基于光敏交联剂A的量子点图案化方法和三色量子点的多色图案化薄膜。选用的红色、绿色、蓝色量子点与实施例1中相同。具体实施步骤如下：
(1)在空气氛围中，取商用硅片作为基底，使用有机溶剂甲苯、丙酮、甲醇与异丙醇分别超声清洗15分钟；在硅片一侧以1500rpm首先转速旋涂红色lnP/ZnS量子点和光敏交联剂A的溶液，溶剂为甲苯，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂A的浓度为1mg/mL；
(2)利用掩模版对红色量子点薄膜进行选择性曝光，曝光光源为365nm，光照剂量为100mJ/cm2，光照时间10s；
(3)将上述量子点薄膜浸泡在甲苯中，未曝光部分量子点从硅片上脱落，选择性曝光的部分显现，得到不再溶解于甲苯的红色阵列图案；
(4)在显现出红色图案的基底上，继续以1500rpm旋涂绿色lnP/ZnS量子点和光敏交联剂A的溶液，溶剂为甲苯，溶液中lnP/ZnS绿色量子点的浓度为30mg/mL，光敏交联剂A的浓度为2mg/mL；
(5)利用掩模版对绿色量子点薄膜进行选择性曝光，曝光光源为365nm，光照剂量为100mJ/cm2，光照时间10s；
(6)将上述量子点薄膜浸泡在甲苯中，未曝光部分量子点从硅片上脱落，选择性曝光的绿色部分显现；
(7)在显现出红色和绿色阵列图案的基底上，继续以1000rpm旋涂蓝色ZnSe/ZnS量子点和光敏交联剂A的溶液，溶剂为甲苯，溶液中ZnSe/ZnS蓝色量子点的浓度为40mg/mL，光敏交联剂A的浓度为2mg/mL；
(8)利用掩模版对蓝色量子点薄膜进行选择性曝光，曝光光源为365nm，光照剂量为100mJ/cm2，光照时间10s；
(9)将上述量子点薄膜浸泡在甲苯中，未曝光部分蓝色量子点从硅片上脱落，选择性曝光的蓝色部分显现，与之前已经交联的红色、绿色阵列图案平行交错排列，如图9所示，单一阵列尺寸为10微米×50微米。
测试例1光敏交联分子的摩尔吸光系数测定
本测试例提供了三种光敏交联剂A、B、C的摩尔吸光系数曲线，如图10所示，三种光敏交联剂分别配置约6×10-4mol/L的溶液，溶剂为甲苯，使用Cary 5000UV-Vis-NIR光谱仪测试相应的紫外吸收度A，利用朗伯比尔定律A＝Kbc计算出摩尔吸光系数K，c为光敏交联剂的浓度，单位为mol/L，b为吸收层厚度1cm，参考此方法依次获得三种光敏交联剂在紫外波段的摩尔吸光系数，量化三种光敏交联剂对紫外波段的吸收能力。
测试例2量子点图案化前后荧光量子产率的比较
本测试例对无镉红色和绿色量子点图案化前后荧光量子产率进行比较。在空气中制备样品，选用的lnP/ZnS红色量子点和lnP/ZnS绿色量子点与实施例1中相同。具体实施步骤如下：
(1)在2cm×2cm石英片上，以1500rpm转速旋涂红色量子点溶液，溶剂为甲苯，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，利用Horiba FluoroMax Plus光谱仪测试此未经过图案化步骤处理的薄膜的荧光量子产率；
(2)在2cm×2cm石英片上，以1500rpm转速旋涂红色量子点和光敏交联剂A的溶液，溶剂为甲苯，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂A的浓度为1mg/mL，利用Horiba FluoroMax Plus光谱仪测试此薄膜的荧光量子产率；
(3)将依照上述步骤(2)方法制得的薄膜进行紫外曝光，光照波长为365nm，光照剂量为200mJ/cm2，光照时间20s，利用Horiba FluoroMax Plus光谱仪测试经过曝光步骤后薄膜的荧光量子产率；
(4)将曝光后的薄膜浸泡在甲苯溶剂中洗脱，用氮气吹干薄膜表面，利用Horiba FluoroMax Plus光谱仪测试经过洗脱步骤后薄膜的荧光量子产率；
类似的，对于绿色lnP/ZnS量子点，测试图案化每一个步骤后薄膜的发光量子产率，旋涂溶液中绿色量子点的浓度为30mg/mL，光敏交联剂A的浓度为2mg/mL，光照波长为365nm,光照剂量为200mJ/cm2，光照时间20s。
结果如图11所示，无论是对于红色还是绿色的lnP/ZnS量子点，均能有较好的荧光量子产率保持，将量子点未经处理的初始薄膜量子产率归一化为100％，在空气中图案化后，红色与绿色lnP/ZnS量子点均具有90％的荧光量子产率保持。
测试例3量子点图案化前后荧光寿命的变化
本测试例考察了量子点图案化前后荧光寿命的变化，在空气中制备样品，选用实施例1中lnP/ZnS红色量子点。具体实施步骤如下：
(1)同样选取2cm×2cm石英片作为基底，以1500rpm转速旋涂lnP/ZnS红色量子点溶液，溶剂为甲苯，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，利用Horiba FluoroMax Plus with time-correlated single photon counting(TCSPC)system测试此未经过图案化步骤处理的薄膜的平均荧光寿命；
(2)选取2cm×2cm石英片，以1500rpm转速旋涂红色量子点和光敏交联剂A的溶液，溶剂为甲苯，溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂A的浓度为1mg/mL，利用Horiba FluoroMax Plus with time-correlated single photon counting(TCSPC)system测试此薄膜的平均荧光寿命；
(3)将步骤(2)制得的薄膜进行紫外曝光，光照波长为365nm,光照剂量为200mJ/cm2，光照时间20s，利用Horiba FluoroMax Plus with time-correlated single photon counting(TCSPC)system测试经过曝光步骤后薄膜的平均荧光寿命；
(4)将曝光后的薄膜浸泡在甲苯溶剂中洗脱，用氮气吹干薄膜表面，利用Horiba FluoroMax Plus with time-correlated single photon counting(TCSPC)system测试经过洗脱步骤后薄膜的平均荧光寿命；
结果如图12所示，对于红色lnP/ZnS量子点经图案化后能有较好的平均荧光寿命保持，量子点未经处理的初始薄膜平均荧光寿命为31.12ns，在混合形成量子点与光敏交联剂薄膜后，平均荧光寿命为31.00ns，紫外曝光后薄膜平均荧光寿命为28.98ns，经过洗脱后薄膜平均荧光寿命为30.59ns。
测试例4镉基量子点图案化前后荧光量子产率的比较
本测试例对一种镉基量子点图案化前后荧光量子产率进行比较，结果如图13所示，量子点选用实施例6中的红色CdSe/Cd1-xZnxSe/ZnSe量子点，具体实施步骤与测试例2中红色InP/ZnS量子点相同，在空气中图案化后，红色CdSe/Cd1-xZnxSe/ZnSe量子点相比于初始薄膜具有80％的荧光产率保持。
测试例5图案化镉基-QLEDs发光显示器件的构筑和相应电学性能评估
本测试例提供了一种图案化镉基-QLEDs发光显示器件的构筑和相应电学性能评估，选用实施例6中的CdSe/Cd1-xZnxSe/ZnSe红色量子点，发光显示器件参照文献Chaoyu Xiang,et al.High efficiency and stability of ink-jet printed quantum dot light emitting diodes.Nat Commun.,2020,11(1):1646所提供的ITO/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate(PEDOT:PSS)/Poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt(4,4’-(N-(4-butylphenyl)))](TFB)/QDs/ZnO/Al结构，如图14中A所示。具体实施步骤如下：
(1)取干净的ITO基底，采用商业玻璃碱性洗液超声洗涤15min，再用去离子水超声清洗15min，重复两次后用无水乙醇超声清洗15min，氮气吹干备用；
(2)将洗净的ITO基底用plasma进行表面处理6min；之后固定在旋涂仪上，在转速4000rpm下旋涂PEDOT：PSS溶液40s，150℃加热退火15min；
(3)在上述基底上旋涂配置好的TFB溶液，2000rpm下旋涂40s，150℃加热退火10min；
(4)在上述基底上继续构筑量子点层(QDs)，配置红色量子点和光敏交联剂A的混合溶液，溶剂为氯苯，溶液中CdSe/Cd1-xZnxSe/ZnSe红色量子点的浓度为10mg/mL，光敏交联剂A的浓度为1mg/mL，在2000rpm转速下旋涂60s，之后利用掩模版对该薄膜进行选择性365nm紫外光照，光照剂量为300mJ/cm2，使量子点表面配体充分交联，利用氯苯溶剂对未发生交联反应的区域进行动态洗脱(2000rpm转速下，在片子上方滴涂50-100μL氯苯)，得到图案化薄膜，在80℃加热退火10min；在进行电学性能测试评估时，发光层构筑的区别在于不使用掩模版，对整个薄膜进行光照处理，避免过大漏电流的影响，从而更好反映此交联图案化方法对器件光电性能的影响。
(5)ZnO的乙醇溶液在2000rpm转速下旋涂40s，在80℃加热退火20min；
(6)将上述器件放置在高真空蒸镀室(压力≤1×10-6mbar)中，热沉积80nm金属Al电极；
(7)利用电源连接器件正负极，点亮实际的QLEDs图案，如图14中B所示的长方形阵列，尺寸为10微米×50微米。
(8)对器件进行电学性能评估，利用紫外线固化树脂对器件进行封装，在空气气氛下使用QE-PRO光谱仪、Keithley 2400等组合，测试QLEDs亮度、电流密度与发光波长等器件参数与性能。图14中C为构筑的图案化红色QLEDs器件的电流密度和发光亮度与电压曲线图；电流密度约为700mA/cm2，发光亮度达到12000cd/m2；图14中D为该图案化QLEDs在不同电压2、3、4、5V下的发光波长，均在620nm处，实际测试点亮发光的QLEDs正方形像素(见图14中D的左下方)，面积为7.25mm2。
测试例6 InP基-QLEDs发光显示器件的构筑和相应电学性能评估
本测试例提供了一种图案化InP基-QLEDs发光显示器件的构筑和相应电学性能评估，选用实施例1中的InP/ZnS红色量子点，发光显示器件结构与测试例5中相同， ITO/PEDOT:PSS/TFB/QDs/ZnO/Al结构，具体实施步骤如下：
(1)取干净的ITO基底，采用商业玻璃碱性洗液超声洗涤15min，再用去离子水超声清洗15min，重复两次后用无水乙醇超声清洗15min，氮气吹干备用；
(2)将洗净的ITO基底用plasma进行表面处理20min；之后固定在旋涂仪上，在转速3000rpm下旋涂PEDOT：PSS溶液30s，150℃加热退火15min；
(3)在上述基底上旋涂配置好的TFB溶液，3000rpm下旋涂40s，150℃加热退火10min；
(4)在上述基底上继续构筑量子点层(QDs)，配置红色量子点和光敏交联剂A的混合溶液，溶剂为辛烷，溶液中红色量子点的浓度为20mg/mL，光敏交联剂A的浓度为1mg/mL，在2000rpm转速下旋涂60s，对整个薄膜进行365nm紫外光照交联，光照剂量为100mJ/cm2，利用辛烷溶剂对进行动态洗脱，在80℃加热退火10min；
(5)ZnO的乙醇溶液在2000rpm转速下旋涂40s，在80℃加热退火20min；
(6)将上述器件放置在高真空蒸镀室(压力≤1×10-6mbar)中，热沉积100nm金属Al电极；
(7)对器件进行电学性能评估，利用紫外线固化树脂对器件进行封装，在空气气氛下使用QE-PRO光谱仪、Keithley 2400等组合，测试QLEDs亮度、电流密度与发光波长等器件参数与性能。图14中E为构筑的图案化红色InP基QLEDs器件的电流密度和发光亮度与电压曲线图；电流密度约为600mA/cm2，发光亮度达到35000cd/m2；图14中F为该图案化QLEDs在不同电压2、3、4、5V下的发光波长，均在620nm处。
测试例7图案化前后荧光量子产率的变化
本测试例考察了一种量子点在一种光敏交联剂作用下图案化前后荧光量子产率的变化，相比于测试例2中，将光敏交联剂A更改为C，将图案化条件更改为溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂C的浓度为2mg/mL，光照剂量为300mJ/cm2，光照时间30s，结果如图15所示，将量子点未经处理的初始薄膜量子产率归一化100％，在空气中利用光敏交联剂C图案化后，红色lnP/ZnS量子点具有较好的80％的产率保持。
测试例8图案化前后荧光寿命的变化
本测试例考察了一种量子点在一种光敏交联剂作用下图案化前后荧光寿命的变化，相比于测试例3中，将光敏交联剂A更改为C，将图案化条件更改为溶液中lnP/ZnS红色量子点的浓度为30mg/mL，光敏交联剂C的浓度为2mg/mL，光照剂量为300mJ/cm2， 光照时间30s，结果如图16所示，图案化步骤不会降低量子点本身的平均荧光寿命，量子点未经处理的初始薄膜平均荧光寿命为31.12ns，图案化最终薄膜平均荧光寿命为28.83ns。
对比例1
本对比例提供了一种图案化量子点薄膜的制备方法，相较于实施例1、3、4中的量子点图案化方法，本对比例区别之处在于：将光敏交联剂由提供的A、B、C替换为3,3'-(4,4'-全氟丁烷-1,4-二基)双(4,1-亚苯基)双(3-三氟甲基)-3H-二吖啶，分子式如下：
该分子合成方法参考已有文献“Shaoyong Lu,et al.Beyond a Linker:The Role of Photochemistry of Crosslinkers in the Direct Optical Patterning of Colloidal Nanocrystals.Angew.Chem.Int.Ed.,2022,61,e202202633”，其制备方法包括以下步骤：
在0℃，氩气条件下，在3,3'-((全氟丁烷-1,4-二基)双(4,1-亚苯基))双(3-(三氟甲基)二氮丙啶)(2.1g)的二氯甲烷溶液(21mL)中10分钟内逐滴滴加三乙胺溶液(3.06mL)，向所得混合物中分三次加入碘单质(2.04g)，并在0℃下继续搅拌2小时，将反应混合物用二氯甲烷(60mL)稀释并转移到分液漏斗中，有机层用水、饱和硫代硫酸钠溶液、水和盐水洗涤，并用硫酸钠干燥。对于该有机层通过硅胶柱色谱法进行纯化，得到所需的亮白色晶体交联分子。
同样在空气中实施，在本对比例中，将部分曝光处理后的lnP/ZnS量子点薄膜浸泡于甲苯中，但并无图案显现(如图17所示)，原因在于：3,3'-(4,4'-全氟丁烷-1,4-二基)双(4,1-亚苯基)双(3-三氟甲基)-3H-二吖啶分子在经过紫外光曝光后产生单线态卡宾中间体，在空气中单线态卡宾易转为三线态并与氧气反应，消耗生成的中间体，未能通过量子点表面配体发生交联作用，而本发明设计的A、B、C分子，由于供电子基团的引入使得中间体单线态向三线态的过程被抑制，即使在空气中，单线态中间体与表面配体也能高效地发生交联作用，实现量子点材料的图案化。
对比例2
本对比例提供了一种量子点在不同光敏交联剂作用下图案化效果，相较于实施例4中的量子点图案化条件，在空气中使用光敏交联剂C，区别在于将紫外光照剂量从300 mJ/cm2替换为50mJ/cm2，将部分曝光处理后的红色lnP/ZnS量子点薄膜浸泡于甲苯中，但并无图案显现(如图18所示)，与实施例1中光敏交联剂A在50mJ/cm2即可实现图案化相比，原因在于光敏交联剂A在365nm波长下摩尔吸光系数大，具有更高的紫外光利用率，光敏交联剂A内存在的三齿交联位点也使交联反应更加高效。

Claims (33)

  1. 一种量子点薄膜图案化方法，其包括以下步骤：
    (1)将量子点与光敏交联剂混合后形成一薄层；
    (2)对所述薄层进行图案化曝光处理，得到图案化的量子点薄膜；
    其中，所述量子点的表面具有含有碳氢键的配体；
    所述光敏交联剂具有式Ⅰ所示的结构：
    式Ⅰ中，R1为供电子基团；n≥2；X为不影响单线态中间体生成的基团。
  2. 根据权利要求1所述的量子点薄膜图案化方法，其中，式Ⅰ中，R1含有烷基氨基、烷氧基、醚基、酰氧基、酰胺基、烷基、亚烷基、羧基甲基、苯基中的一种或两种以上的结构；所述n为2、3或4；X选自H、卤素、羟基、烷基及其衍生物、烷氧基及其衍生物、氨基、腈基。
  3. 根据权利要求2所述的量子点薄膜图案化方法，其中，X选自-Cl、-F、-OH、-H、-CH3、-CF3、-OCH3、-NH2或-CN。
  4. 根据权利要求2所述的量子点薄膜图案化方法，其中，R1含有苯基、醚基、亚烷基中的一种或两种以上的结构；n为2、3或4；X选自-CF3。
  5. 根据权利要求2所述的量子点薄膜图案化方法，其中，所述光敏交联剂的碳原子数为1-100，分子量为100-10000。
  6. 根据权利要求2所述的量子点薄膜图案化方法，其中，所述光敏交联剂选自

    中的一种或两种以上的组合。
  7. 根据权利要求1所述的量子点薄膜图案化方法，其中，所述量子点的材料包括II-VI族化合物、III-V族化合物、IV-VI族化合物、I-III-VI族化合物、钙钛矿纳米晶体中的一种或两种以上的组合。
  8. 根据权利要求7所述的量子点薄膜图案化方法，其中，所述量子点为核壳结构的量子点。
  9. 根据权利要求7所述的量子点薄膜图案化方法，其中，所述II-VI族化合物包括CdSe、CdS、CdTe、CdxSe1-xS、CdxSe1-xTe、ZnO、ZnSe、ZnS、ZnTe、ZnxSe1-xS、ZnxSe1-xTe、CdxZn1-xSe、CdxZn1-xS、CdxZn1-xTe、HgSe、HgS、HgTe、HgxCd1-xSe、HgxCd1-xS、HgxCd1-xTe中的一种或两种以上的组合，其中，0＜x＜1。
  10. 根据权利要求7所述的量子点薄膜图案化方法，其中，所述III-V族化合物包括lnP、InAs、InSb、InN、GaP、GaAs、GaSb、GaN、AlP、AlAs、AlSb、AlN中的一种或两种以上的组合。
  11. 根据权利要求7所述的量子点薄膜图案化方法，其中，所述IV-VI族化合物包括PbS、PbSe、PbTe、PbxSe1-xS、PbxSe1-xTe、SnS、SnSe、SnTe、SnxSe1-xS、SnxSe1-xTe 中的一种或两种以上的组合，其中，0＜x＜1。
  12. 根据权利要求7所述的量子点薄膜图案化方法，其中，所述I-III-VI族化合物包括CuInS2、CuInSe2、AgInS2中的一种或两种以上的组合。
  13. 根据权利要求7所述的量子点薄膜图案化方法，其中，所述钙钛矿纳米晶体包括CsPbY3、CH3NH3PbY3、FAPbY3、MAPbY3中的一种或两种以上的组合，其中，Y选自Cl、Br或I。
  14. 根据权利要求1所述的量子点薄膜图案化方法，其中，所述量子点的表面配体的碳原子数为3-30。
  15. 根据权利要求1所述的量子点薄膜图案化方法，其中，所述量子点的表面配体的主链含有碳氢键。
  16. 根据权利要求1所述的量子点薄膜图案化方法，其中，所述量子点的表面配体含有硫醇、羧酸、胺、膦、膦酸中的一种或两种以上的结构。
  17. 根据权利要求1所述的量子点薄膜图案化方法，其中，所述量子点的表面配体包括油胺、油酸、十八胺、1-十二烷硫醇、三辛基膦、十八烷基膦酸中的一种或两种以上的组合。
  18. 根据权利要求1所述的量子点薄膜图案化方法，其中，步骤(1)中，将量子点与光敏交联剂混合于溶剂中得到溶液，将该溶液形成一薄层；其中，所述溶液中的量子点的浓度为5-1000mg/ml，量子点与添加的光敏交联剂的质量浓度比为1：(0.01-1)。
  19. 根据权利要求18所述的量子点薄膜图案化方法，其中，所述溶液的溶剂选自甲苯、氯苯、正己烷、正辛烷、正庚烷、环己烷、二氯甲烷、氯仿、四氢呋喃中的一种或两种以上的组合。
  20. 根据权利要求1所述的量子点薄膜图案化方法，其中，所述光敏交联剂在曝光处理波长下的摩尔吸光系数为10cm-1M-1至106cm-1M-1。
  21. 根据权利要求1所述的量子点薄膜图案化方法，其中，所述量子点薄膜图案化方法的各个步骤分别在空气、氮气或氩气中进行实施。
  22. 根据权利要求1所述的量子点薄膜图案化方法，其中，步骤(2)中，所述曝光处理的波长为100-500nm，光照剂量为1-5000mJ/cm2。
  23. 根据权利要求1所述的量子点薄膜图案化方法，其中，在对所述薄层进行曝光处理后，采用洗脱溶剂去除未发生交联的原料，所述洗脱溶剂为非极性溶剂。
  24. 根据权利要求23所述的量子点薄膜图案化方法，其中，所述非极性溶剂包括甲 苯、氯苯、正己烷、正辛烷、正庚烷、环己烷、二氯甲烷、氯仿、四氢呋喃中的一种或两种以上的组合。
  25. 由权利要求1-24任一项所述的量子点薄膜图案化方法制得的图案化的量子点薄膜。
  26. 一种光电器件，其结构组成包含阳极、阴极、量子点发光层，其中，所述量子点发光层为权利要求25所述的图案化的量子点薄膜或者由权利要求1-24任一项所述的量子点薄膜图案化方法制得。
  27. 根据权利要求26所述的光电器件，其中，所述量子点发光层位于阴极与阳极之间，所述阳极和所述阴极的材料各自独立地选自金属或碳材料；所述金属选自Al、Ag、Au、Cu、Mo、Mg、Ba、Ca中的一种或两种以上的组合，所述碳材料选自碳纳米管、石墨、石墨烯、碳纤维中的一种或两种以上的组合。
  28. 根据权利要求27所述的光电器件，其中，所述光电器件的结构组成还包含电子注入层、空穴注入层、电子传输层、空穴传输层，所述电子注入层和电子传输层位于阴极与所述量子点发光层之间，所述电子注入层靠近阴极的一侧，所述电子传输层靠近所述量子点发光层；所述空穴注入层和空穴传输层位于阳极和所述量子点发光层之间，所述空穴注入层靠近阳极的一侧，所述空穴传输层靠近所述量子点发光层的一侧。
  29. 根据权利要求28所述的光电器件，其中，所述电子注入层的材料包括碱金属卤化物、碱金属有机络合物、有机氧化磷、有机硫代膦化合物、有机硒代膦化合物中的一种或两种以上的组合。
  30. 根据权利要求28所述的光电器件，其中，所述电子传输层的材料包括单一金属氧化物和/或掺杂金属氧化物，所述单一金属氧化物选自ZnO、ZrO2、SnO2、BaO、TiO2、Ta2O3中的一种或两种以上的组合；所述掺杂金属氧化物为所述单一金属氧化物掺杂Al、Li、Ga、Mg、Sn、In、F、Cl中的一种或两种以上的元素。
  31. 根据权利要求28所述的光电器件，其中，所述空穴注入层的材料选自聚(3,4-乙烯二氧基噻吩)、聚(苯乙烯磺酸)、4,4',4'-三(N-3-甲基苯基-N-苯基氨基)三苯胺、4,4',4'-三(2-萘基苯基氨基)三苯胺、1,4,5,8,9,12-六氮杂三苯-2,3,6,7,10,11-六腈、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌、NiO、MoO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、CuS、WS2中的一种或两种以上的组合。
  32. 根据权利要求28所述的光电器件，其中，所述空穴传输层的材料选自聚(3-己基噻吩-2,5-二基)、聚(9-乙烯咔唑)、聚[[(2,4-二甲基苯基)亚氨基]-1,4-亚苯基(9,9-二辛基 -9H-芴-2,7-二基)-1,4-亚苯基]、聚(9,9-二辛基芴-2,7-二基)、聚[双(4-苯基)(4-丁基苯基)胺]、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(4-叔丁基苯基)二苯胺)]、聚[9,9-二辛基芴-双-N,N-(4-丁基苯基)-双-N,N-苯基-1,4-苯二胺]、三[4-(咔唑-9-基)苯基]胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺、聚(3,4-乙烯二氧基噻吩)、聚(苯乙烯磺酸)、石墨烯、NiO、WO3、CuI、CuSCN、CuO、CuInS2、GaN、C60、MoO3、V2O5、CrO3中的一种或两种以上的组合。
  33. 根据权利要求26-32任一项所述的光电器件，其中，所述光电器件为阵列式光电器件。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106715399A (zh) * 2014-09-23 2017-05-24 普罗米鲁斯有限责任公司 作为光交联剂的二氮杂环丙烯化合物以及包含二氮杂环丙烯化合物的可光成像组合物
CN114839835A (zh) * 2022-03-18 2022-08-02 清华大学 量子点的无损光刻图案化方法和设备
WO2022187932A1 (en) * 2021-03-09 2022-09-15 Xlynx Materials Inc. Aryl ether diazirines for use in polymer crosslinking and adhesion

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111781803B (zh) * 2020-06-24 2021-10-26 清华大学 量子点薄膜的无光刻胶光致图案化方法
CN113972345A (zh) * 2020-07-22 2022-01-25 Tcl科技集团股份有限公司 量子点发光二极管及其制备方法
CN114242923A (zh) * 2021-11-12 2022-03-25 华南理工大学 一种硫醇类化合物界面修饰磷化铟量子点提高电致发光器件性能的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106715399A (zh) * 2014-09-23 2017-05-24 普罗米鲁斯有限责任公司 作为光交联剂的二氮杂环丙烯化合物以及包含二氮杂环丙烯化合物的可光成像组合物
WO2022187932A1 (en) * 2021-03-09 2022-09-15 Xlynx Materials Inc. Aryl ether diazirines for use in polymer crosslinking and adhesion
CN114839835A (zh) * 2022-03-18 2022-08-02 清华大学 量子点的无损光刻图案化方法和设备

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LU SHAOYONG, FU ZHONG, LI FU, WENG KANGKANG, ZHOU LIKUAN, ZHANG LIPENG, YANG YUCHEN, QIU HENGWEI, LIU DAN, QING WENYUE, DING HE, S: "Beyond a Linker: The Role of Photochemistry of Crosslinkers in the Direct Optical Patterning of Colloidal Nanocrystals", ANGEWANDTE CHEMIE, VERLAG CHEMIE, HOBOKEN, USA, vol. 61, no. 23, 7 June 2022 (2022-06-07), Hoboken, USA, pages e202202633, XP093279239, ISSN: 1433-7851, DOI: 10.1002/anie.202202633 *
MUSOLINO STEFANIA F., PEI ZHIPENG, BI LITING, DILABIO GINO A., WULFF JEREMY E.: "Structure–function relationships in aryl diazirines reveal optimal design features to maximize C–H insertion", CHEMICAL SCIENCE, ROYAL SOCIETY OF CHEMISTRY, UNITED KINGDOM, vol. 12, no. 36, 22 September 2021 (2021-09-22), United Kingdom , pages 12138 - 12148, XP093279237, ISSN: 2041-6520, DOI: 10.1039/D1SC03631A *

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